CN100409476C - Fuel cell power generating system - Google Patents
Fuel cell power generating system Download PDFInfo
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- CN100409476C CN100409476C CNB200510109934XA CN200510109934A CN100409476C CN 100409476 C CN100409476 C CN 100409476C CN B200510109934X A CNB200510109934X A CN B200510109934XA CN 200510109934 A CN200510109934 A CN 200510109934A CN 100409476 C CN100409476 C CN 100409476C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
- H01M8/04179—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal by purging or increasing flow or pressure of reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides a full cell power generation system. In a conventional fuel cell power generation system having a function for producing nitrogen gas, a deoxidation material having a deoxidation reaction speed sufficient for a flow rate of an oxygen-containing gas flowing through an oxygen remover must be used. This fuel cell power generation system is provided with:a fuel cell 1 for generating power by using hydrogen; the fuel reformer 2 which provides hydrogen to the fuel cell 1 ; a tank 8 including the deoxidation material 15 for removing oxygen in a gas while storing the gas; a pressurization means 13 for pressurizing the oxygen-containing gas to supply it to the tank 8; an inactive gas pipe 16 for connecting the fuel reformer 2 or the fuel cell 1 to the tank 8; and a cutoff valve 17 installed in an intermediate part of the inactive gas pipe 16.
Description
Technical field
The reduction that the present invention relates to when stopping the displacement of imflammable gas in the adjoint system or temperature for anti-locking system cause in system, attracting air and use have a fuel cell generation that in self system, makes the function of nitrogen.
Background technology
In existing fuel cell generation, the displacement of imflammable gas in the adjoint system (drive imflammable gas away, fill inactive gas) or the reduction of temperature cause attracting air etc. when stopping for anti-locking system, have the torpescence gas cylinder.
Have the fuel cell generation of torpescence gas cylinder, cause the increase of optional equipment and the burden of gas delivery.Therefore, studied and had the fuel cell generation that in self system, makes the function of inactive gas, for example constitute such structure: utilize the deaerator that uses deoxidation material, oxygen-containing gas (burning and gas-exhausting) is flow through, carry out deoxidation treatment, the inactive gas (nitrogen) that generates is accumulated in the storage tank, is used for the displacement of imflammable gas in the system etc.(for example patent documentation 1).
[patent documentation 1]
The flat 6-203865 communique of Japanese Patent Application Laid-Open
In existing fuel cell generation with the function that makes nitrogen, be necessary to use flow corresponding to the oxygen-containing gas that flows through deaerator, the deoxidation material of sufficient deoxygenation speed is arranged.In addition,, uses repeatedly deoxidation material, so can reduce the performance of deoxidation material because being carried out redox.Therefore, there is the problem need high-performance and a large amount of deoxidation material.
The present invention finishes in order to solve described problem, and purpose is not need to use high performance deoxidation material.
Summary of the invention
Fuel cell generation of the present invention has: the fuel cell that uses hydrogen to generate electricity; Hydrogen is supplied with the hydrogen feed unit of this fuel cell; Deoxidation material is equipped with in inside, and stored gas and meanwhile with the oxygen in the gas remove the jar; Oxygen-containing gas is boosted and supply with above-mentioned jar boosting unit; The inactive gas pipeline that above-mentioned fuel cell or above-mentioned hydrogen feed unit at least one and the above-mentioned jar among both coupled together; And be arranged on this inactive gas pipeline cut-off valve midway.
Because fuel cell generation of the present invention has: the fuel cell that uses hydrogen to generate electricity; Hydrogen is supplied with the hydrogen feed unit of this fuel cell; Deoxidation material is equipped with in inside, and stored gas and meanwhile with the oxygen in the gas remove the jar; Oxygen-containing gas is boosted and supply with above-mentioned jar boosting unit; The inactive gas pipeline that above-mentioned fuel cell or above-mentioned hydrogen feed unit at least one and the above-mentioned jar among both coupled together; And be arranged on this inactive gas pipeline cut-off valve midway, can increase the deoxidation material that helps deoxidation treatment and the time of contact of oxygen-containing gas significantly so have, even use the low deoxidation material of deoxygenation speed, also can carry out the effect of deoxidation treatment fully.
Description of drawings
Fig. 1 is the block diagram of structure of the fuel cell generation of explanation embodiments of the present invention 1.
Fig. 2 is the block diagram of structure of the fuel cell generation of explanation embodiments of the present invention 2.
Fig. 3 is the block diagram of structure of the fuel cell generation of explanation embodiments of the present invention 3.
(Reference numeral)
1: polymer electrolyte fuel cell (fuel cell) 1A: anode 1B: negative electrode
2: fuel modifying device 2A: burner 3: town gas feed system
4: water system 5; Raw material supplying pipeline 6: fuel gas supply pipeline
7: air supply system 8: jar 9: anode exhaust service
10: cut-off valve 11: cut-off valve 12: cut-off valve 13: compressor
14: cut-off valve 15: deoxidation material 16: deoxidation nitrogen service (inactive gas pipeline) 17: cut-off valve 18: cut-off valve
19: reducing gas service (reducing gas pipeline)
20: reducing gas discharge line 21: cut-off valve
22: burning and gas-exhausting service (burning and gas-exhausting pipeline)
23: pressure gauge (piezometry unit) 24: computing circuit
25: displacement can 26: normal temperature jar (second jar) 27: cut-off valve (second cut-off valve)
Embodiment
(execution mode 1)
Fig. 1 is the block diagram of structure of the fuel cell generation of explanation embodiments of the present invention 1.This fuel cell generation is imagined for example big place of power consumption on daytime such as shop or company, and daytime, generating was used.Therefore, fuel cell generation all starts and stops every day, and the inactive gas that uses when manufacturing system stops at an easy rate is important.
Fuel cell generation is made of following part: as the polymer electrolyte fuel cell 1 of the fuel cell that uses the hydrogen generating; By steam upgrading reaction, town gas is transformed into fuel modifying device 2 based on the fuel gas of hydrogen; Will be as the town gas feed system 3 of the town gas fueling modifier 2 of raw material; Water system 4 with water fueling modifier 2; Town gas and water are mixed, make it flow through the raw material supplying pipeline 5 of fuel modifying device 2; Make in fuel modifying device 2 the fuel gas that takes place flow to fuel gas supply pipeline 6 in the polymer electrolyte fuel cell 1 based on hydrogen; Air is supplied with the air supply system 7 of polymer electrolyte fuel cell 1; And the displacement of imflammable gas or the temperature air attraction that takes place etc. that descends in the adjoint system when stopping for anti-locking system, store the jar 8 of the inactive gas of supplying with to polymer electrolyte fuel cell 1 and fuel modifying device 2 etc.
Be supplied to fuel modifying device 2 after mixing as the town gas of raw material and water, by the reaction of steam upgrading, will be based on the anode 1A of the fuel gas supply polymer electrolyte fuel cell 1 of hydrogen.On the other hand, by air supply system 7 air is supplied with the negative electrode 1B of polymer electrolyte fuel cell 1.In polymer electrolyte fuel cell 1, hydrogen and airborne oxygen react according to following reaction equation and generate electricity.
H
2→2H
++2e
- (1)
1/2×O
2+2H
++2e
-→H
2O (2)
Reaction shown in (1) formula takes place on anode 1A, and the electronics that is taken place is fetched to the outside, as the electricity utilization.Electronics after being utilized is supplied to negative electrode 1B, with the hydrogen ion (H that moves in polymer electrolyte fuel cell 1
+) and oxygen cause the reaction shown in (2) formula.
The generation of the hydrogen that is caused by the steam upgrading in the fuel modifying device 2 reaction takes place under about 700 ℃ temperature, also needs reaction heat.Come supply response heat for fuel modifying device 2 being heated to about 700 ℃, in fuel modifying device 2, have burner 2A, utilize this burner 2A, make hydrogeneous anode exhaust burning.For with anode exhaust supplied burner 2A, and anode exhaust service 9 is arranged.
Can to stop in order stopping to supply with town gas and water, between town gas feed system 3 and raw material supplying pipeline 5, cut-off valve 10 to be arranged, in the middle of water system 4 and raw material supplying pipeline 5, cut-off valve 11 be arranged to fuel modifying device 2 in system.In addition, in anode exhaust service 9, the cut-off valve 12 that blocking-up anode exhaust air-flow is used when having system to stop.If air was sneaked in the fuel modifying device 2 when system stopped, then will becoming because the oxidized decreased performance that causes of catalyst, so nitrogen is enclosed in the system when system stops.Here, the cut-off valve 12 that has of the downstream of cut-off valve 10 that will have from the upstream of raw material supplying pipeline 5 and the cut-off valve 11 anode 1A of fuel cell 1 to the downstream is called in the system.
Utilization is as the compressor 13 of boosting unit, makes the i.e. compression of boosting of air as oxygen-containing gas, is stored in jars 8 by cut-off valve 14.When generated output was the 10kW left and right sides, the capacity of jar 8 was number L.
Deoxidation material 15 is filled in the inside of jar 8.Adopt the material of oxygen being removed after the oxidation voluntarily of shaping thing and so on of for example metal dust such as copper or iron, nickel, metal derby or metal dust and pottery in the deoxidation material 15.Jars 8 with the 2 adjacent settings of fuel modifying device so that the heat of conduction fuel modifying device 2, when fuel modifying device 2 and polymer electrolyte fuel cell 1 work, keep 100 ℃ temperature for example to be arranged on the position of suitable regulation for making deoxidation materials 15 in jars 8.The position of this regulation is that benchmark decides with any one or both in fuel modifying device 2 or the polymer electrolyte fuel cell 1.Consider the performance of oxidation, the needed catalyst of reduction, set the working temperature of deoxidation material 15.At the inner utilization deoxidation material 15 of jar 8, what oxygen had been removed from air is that the gas of main component is called as deoxidation nitrogen with nitrogen.Deoxidation nitrogen is inactive gas.
Like this,, utilize the heat that takes place in the fuel cell system, do not need new thermal source, can improve the energy efficiency of fuel cell system effectively as in jar 8, forming the oxidation reaction that causes by deoxidation material 15 and the temperature conditions of reduction reaction effectively.
In addition, use the part of fuel gas in order to make deoxidation material 15 reduction (oxygen is separated), for this reason, have after the branch midway of fuel gas supply pipeline 6 to enter jars 8 reducing gas service 19 by cut-off valve 18 as the reducing gas pipeline; And make the gas that comes out from jar 8 the reducing gas discharge line 20 that returns midway at anode exhaust service 9.Cut-off valve 21 is arranged in the reducing gas discharge line 20.
The following describes working condition.About being filled in the reduction and the deoxidation treatment of the deoxidation material 15 in jars 8,, below provide an example though can carry out work according to various orders.
In order to make deoxidation material 15 reduction, in the work of fuel modifying device 2, in the stipulated time about tens of minutes to a few hours, cut-off valve 18 and cut-off valve 21 are opened, cut-off valve 14 and cut-off valve 17 are closed.During such state, be supplied to jars 8 based on the part of the fuel gas of hydrogen.Deoxidation material 15 utilizes fuel gas to reduce, and recovers the function as deoxidation material 15.The hydrogen of the unreacted portion of coming out from jar 8 burns among burner 2A.In reducing gas service 19 or reducing gas discharge line 20, be provided with flow regulating unit (not shown)s such as orifice plate, set suitable flow so that reduction reaction is unlikely to excessive or not enough, be expected to improve the efficient of fuel cell system.
After deoxidation material 15 reduction, close cut-off valve 18 and cut-off valve 21, open cut-off valve 14, with compressor 13 compressed air and supplying tank 8.With air supplying tank 8 and after reaching upper limit pressure (for example 10 atmospheric pressure), compressor 13 is stopped, closing cut-off valve 14.The air that is supplied to jar 8 utilizes deoxidation material 15 to carry out deoxidation treatment, and being transformed into inactive gas is deoxidation nitrogen, is stored in the jar 8.
After the deoxidation treatment, because oxygen has been removed, so the upper limit pressure the when gas pressures in jars 8 are supplied with than air is low.Suppose that airborne oxygen concentration is α (, being assumed to be 20% here), if oxygen roughly is removed, then pressure also drops to (1-α) doubly.If dropped to the pressure of regulation, then open cut-off valve 14 once more, with compressor 13 compressed air and supplying tank 8.With air supplying tank 8 and after reaching upper limit pressure, compressor 13 is stopped, closing cut-off valve 14, carry out such work repeatedly, can will be stored in the jar 8 near the nitrogen of upper limit pressure.Then, wait jar 8 interior deoxidation treatment of being undertaken by deoxidation material 15 finish, in case finish, just have been full of deoxidation nitrogen in the jar 8.
When filling air for the first time, fill the air of the amount of capacity of jar 8 with the upper limit pressure of jar 8.For the second time, the air of the oxygen equal number of filling and being removed is so the air capacity of filling reduces gradually.Suppose speed that deoxidation material 15 removes deoxidation contacts deoxidation material 15 with oxygen probability promptly with the proportional relation of oxygen concentration, to the interior oxygen concentration of jar 8, the logarithm and the time of oxygen concentration reduce pro rata so.Therefore, oxygen reach the doubly needed time of β after the filling (for example 0.1) and oxygen concentration irrelevant but certain.If the doubly needed time of β that oxygen reaches after the filling is T (for example 2 minutes), supposing to fill the needed time of air is zero, carried out the supply of n air after filling during elapsed time T repeatedly, establishing the intact back of firm filling oxygen concentration so is C (n), when oxygen concentration is D (n) before filling next time, following relation is arranged.
At first, owing to utilizing deoxidation material 15, oxygen in jar 8 is removed, so become following appearance.
D(n)＝β×C(n) (3)
Replace the oxygen removed by deoxidation material 15 owing to fill air, so become following appearance.
C(n+1)＝D(n)+(C(n)-D(n))×α (4)
According to (3) formula and (4) formula, first back C (the 1)=α that fills is so become following appearance.
C(n)＝(β+(1-β)×α)
n-1×α (5)
D(n)＝(β+(1-β)×α)
n-1×α×β (6)
Behind the deoxygenation EO, the difference of the pressure of gas and upper limit pressure is in γ (for example 1%) in jar, and for gas being filled in jars 8, needed filling number of repetition N is the n that is reached the following minimum of γ by the C (n) that (5) formula is calculated.Suppose β=0.1, N=3 then, even β=0.01, same N=3.Under the situation of β=0.01, T is 2 times of T of β=0.1 o'clock, so the time the during end-of-fill repeatedly of air can more early be finished filling under the situation of β=0.1.In addition, fills with air is needed several seconds to time of tens of seconds in jars 8, in the process of fills with air in the jar 8, also can utilize deoxidation material 15 to carry out removing of oxygen,, but we can say roughly the same so following formula may not still be set up.
Deoxidation nitrogen with making in the jar 8 and being in store is used for the displacement of the inactive gas in the fuel cell generation when generating stops, the vacuum suction when perhaps stopping for anti-locking system, and be used for replenishing of inactive gas.
The displacement of intrasystem inactive gas is carried out according to the following steps: close cut-off valve 10 and cut-off valve 11 when fuel cell system stops, stopping the supply of raw material, open cut-off valve 17, make deoxidation nitrogen flow into raw material supplying pipeline 5 from deoxidation nitrogen service 16.In deoxidation nitrogen service 16, be provided with flow regulating unit (not shown)s such as orifice plate, can regulate the flow of deoxidation nitrogen.In addition, when not only fuel cell system stops, and also can implement the displacement of inactive gas when starting.
After with inactive gas system being full of, deoxidation nitrogen that also just are stored in jars 8 circulate in system.This is that the burning among the burner 2A also stops because in a single day system stops, so the overall temperature of fuel cell system reduces, because temperature reduces, so intrasystem pressure reduces, prevents from air is attracted in the system.After temperature fully reduces, cut-off valve 12 and cut-off valve 17 are closed.Before temperature fully reduces, also can close cut-off valve 12 and cut-off valve 17, make and become seal cavity in the system, by pressure regulating mechanism etc., with than the high pressure of atmospheric pressure with in the deoxidation nitrogen feed system, even pressure is followed temperature to reduce and after reducing, also can be reached the suitable pressure higher than atmospheric pressure.
In this execution mode 1, deoxidation material 15 is arranged in the jar 8, the oxygen-containing gas that pressurization is stored carries out deoxidation treatment.The method that method of the present invention is called stationary system.Different therewith, in the past make oxygen-containing gas flow through deoxidation material 15 to carry out deoxidation treatment, will ensconce in the jar, such method is called the method for the system for the distribution of commodities by the deoxidation nitrogen storage that deoxidation treatment generates.
In the method for stationary system, can increase the deoxidation material 15 that helps deoxidation treatment and the time of contact of oxygen-containing gas significantly, with the low deoxidation material 15 of deoxygenation speed, also can carry out deoxidation treatment fully.Therefore do not need to use high performance deoxidation material 15, in addition, can also reduce the use amount of deoxidation material 15.
The following amount of the needed deoxidation material 15 of deoxygenation in the method for explanation method of the system for the distribution of commodities and stationary system.The basic condition of deoxygenation at first, is described.Deoxidation material 15 is to be configured absorbing the method for disperseing on the material space of oxygen.In this execution mode 1, use the copper catalyst series, under 100 ℃ temperature, carry out deoxygenation.The volume that the deoxidation material 15 of 150g occupies is approximately 0.15L, if the deoxidation material 15 of air contact 150g reaches 1 minute and 30 seconds, then oxygen concentration reduces to 0.1%.No matter be the system for the distribution of commodities or stationary system, if contact the identical time with the deoxidation material of the identical performance of same amount, then oxygen concentration reduces same degree.
In the system for the distribution of commodities, carry out under the situation of deoxidation treatment at the oxygen remover that uses maintenance to occupy the 150g deoxidation material 15 of about 0.15L volume, if make air mobile with 0.1L/ minute speed, the 5L air is flow through need 50 minutes, the time average that air is detained in the oxygen remover is 1 minute and 30 seconds, so the oxygen concentration of the gas that comes out from the oxygen remover is 0.1%.Need carry out under the situation of deoxidation treatment with the shorter time, be necessary to increase the amount of the capacity and the deoxidation material 15 of oxygen remover.For example, the weight of deoxidation material 15 and possessive volume thereof are increased 10 times, in the oxygen remover that uses 1500g deoxidation material 15, the oxygen concentration that flows out when air is flowed with 1L/ minute speed in the gas of oxygen remover is 0.1%.
In the method for stationary system, consider in the jar 8 of 0.5L volume, to dispose the 150g deoxidation material that occupies about 0.15L volume, fill the situation that 100 ℃ of 10 atmospheric air carry out deoxidation treatment.In the case, be equivalent to the fills with air of 100 ℃ of 1 atmospheric pressure 5L has been arrived in the jar 8, the time ratio that gases in the jar 8 contact with deoxidation material 15 is 0.15/0.5=0.3, so from filling after air counts 5 minutes, the mean value of the time of air contact deoxidation material 15 is 1 minute and 30 seconds, and jar 8 interior oxygen concentrations become 0.1%.As time goes by, oxygen concentration further descends.In addition, carry out at spended time under the situation of deoxidation treatment, also can use the deoxidation material 15 of less amount.For example, count 50 minutes from filling after, making oxygen concentration is 0.1% o'clock, the 15g deoxidation material gets final product in the method for stationary system.
Like this in the method for stationary system, because the air of deoxidation material contact compression, so the amount of the gas of contact deoxidation material can be bigger than the situation of the method for the system for the distribution of commodities, can be littler with the amount of the needed deoxidation material of gas after the deoxidation of identical time generation same amount than the situation of the method for the system for the distribution of commodities.In the method for stationary system, be stored in jars 8 during carry out deoxidation treatment, so can carry out deoxidation treatment with the longer time, under the cost situation of longer time, the deoxidation material of usefulness less amount gets final product.
In addition, in the method for stationary system, also can use the slow-footed deoxidation material of deoxygenation, need not high performance dispersed metal carried catalyst, also can use the clipped wire of more cheap porous etc.
In the present embodiment, show for example that to have fuel such as town gas be that hydrocarbon is transformed into the fuel cell generation based on the fuel modifying device of the fuel gas of hydrogen, but in the fuel cell generation that hydrogen is supplied to fuel cell by hydrogen supply system, also can be suitable for as the hydrogen feed unit.
In addition, middle pipeline and the cut-off valves that use such as displacement by intrasystem inactive gas carries out also can use the pipeline and the cut-off valve of the fuel gas circulation of using in the reduction of deoxidation material 15 by double as.For example, do not have deoxidation nitrogen service 16 and cut-off valve 17,, close cut-off valve 21, can replace etc. yet by intrasystem inactive gas by opening cut-off valve 18.In addition, also deoxidation nitrogen service 16 and cut-off valve 17 can be arranged still, open cut-off valve 17 and cut-off valve 18 both, in the inactive gas feed system.
In the present embodiment, though when deoxidation material 15 reduction, will give burner 2A, the entrance side of anode 1A that also can the fueling battery from the gas that jar 8 comes out.In addition, not that cut-off valve 18 is often opened during deoxidation material 15 reduction, but close cut-off valve 18 termly, can reduce yet with being trapped in jar 8 interior hydrogen.Thus, hydrogen can be used for reduction reaction effectively.In addition, the hydrogen in the last usefulness that reduction is handled is trapped in jar 8 reduces, and reduces the hydrogen concentration in the jar 8, when supplying with the oxygen-containing gas that supplies deoxidation, can reduce the possibility that oxygen and hydrogen sharply react, and more can seek safe.Carry out deoxidation treatment if close cut-off valve 18, then can prevent the rising of the hydrogen concentration that the diffusion by fuel gas causes, more effective.The effect of the gas generation of supply reduction usefulness is identical with the situation of using hydrogen gas in addition off and on.
Though generate the order of deoxidation nitrogen when having provided the generating work of fuel cell generation here, if but deoxidation material 15 is the reducing condition with deoxygenation function, then can carry out the generation of deoxidation nitrogen at any time, when for example generating stops back or fuel cell generation startup, also can generate deoxidation nitrogen.In addition, also can generate deoxidation nitrogen in a plurality of moment.
Above situation also is suitable in other execution mode.
(execution mode 2)
Fig. 2 is the structured flowchart of the fuel cell generation of explanation embodiments of the present invention 2.In execution mode 2, the burning and gas-exhausting that uses the oxygen concentration gas lower than air promptly to discharge from fuel modifying device 2 constitutes the oxygen-containing gas of using when generating deoxidation nitrogen.
The different place of Fig. 1 under explanation and execution mode 1 situation only.Appended the burning and gas-exhausting service 22 in the part input compressor 13 of the exhaust of fuel modifying device 2 as combustion gas pipe.Also appended: the pressure gauge 23 of measuring the stored gas pressure in the jar 8 as the piezometry unit; The pressure that input is measured with pressure gauge 23, the computing circuit 24 of calculating the reaction speed of deoxidation material 15; And collection is present in the displacement can midway 25 that is arranged on deoxidation nitrogen service 16 of the condensed water in the jar 8.
The following describes work.Similarly carry out the reduction of deoxidation material 15 with execution mode 1.After deoxidation material 15 reduction, close cut-off valve 18 and cut-off valve 21, open cut-off valve 14.With the part of compressor 13 compressions from the exhaust of the fuel modifying device 2 of burning and gas-exhausting service 22 supplies, and supplying tank 8.With the temperature data of measuring in advance,, calculate the reaction speed of deoxidation material 15 on one side with computing circuit 24 according to the data that the pressure of measuring with pressure gauge 23 changes, with execution mode 1 similarly carry out deoxidation treatment on one side.The reaction speed of the deoxidation material 15 of calculating is counted as judges whether deoxidation material 15 is keeping the foundation of performance fully.
When oxygen-containing gas supplying tank 8 was carried out deoxidation treatment, along with the carrying out of deoxygenation, the pressure of stored gas descended.In other words, the pressure of time per unit descends proportional with the reaction speed of deoxidation material 15.Because deoxidation material 15 carries out redox repeatedly, so deoxy performance descends.Under the situation that the oxidation reaction speed of deoxidation material 15 has descended, the pressure decrease speeds in jars 8 reduce.Therefore, be input in the computing circuit 24, calculate the reaction speed of deoxidation material 15, can judge the necessity that the decline of following catalyst performance is changed by descending by the pressure that pressure gauge 23 is measured.In order to judge more accurately, also can measure the information relevant such as variations in temperature of stored gas, correction arithmetic circuit 24 with pressure condition.
Identical with execution mode 1, when stopping, opening fuel cell system cut-off valve 17, and make deoxidation nitrogen flow through raw material supplying pipeline 5 from deoxidation nitrogen service 16, carry out the displacement of being undertaken by intrasystem inactive gas.Since deoxidation nitrogen service 16 be provided with displacement can 25 midway, so the condensed waters that generate in the jar 8 can be discharged into jar 8 outsides.
In this embodiment, owing to adopt the deoxygenation that carries out according to the method for stationary system, so compare with the method for the system for the distribution of commodities, can increase the deoxidation material that helps deoxidation treatment and the time of contact of oxygen-containing gas significantly, also can use the slow-footed deoxidation material of deoxygenation, can reduce the use amount of the needed deoxidation material of deoxygenation.
The burning and gas-exhausting of discharging from fuel modifying device 2 is the oxygen concentration gas lower than air, so more can shorten the time of the deoxidation treatment in jars 8, under identical situation of the time of deoxidation treatment, the amount of the deoxidation material 15 that needs can be still less.
In addition, owing to have the computing circuit 24 that calculates reaction speed, so can judge whether to be necessary to change deoxidation material 15 exactly.
Though used burning gases in the present embodiment, use the oxygen concentration gas lower that in system, generates than air, can obtain same effect, for example, also can use the cathode exhaust gas of fuel cell.In addition, the supplying tank 8 that also any one or both and air mixed in burning gases and the cathode exhaust gas can be got up.In addition, under the situation of supplying with moisture oxygen-containing gas, before boosting, preferably carry out aqueous vapor and separate with compressor.
In the present embodiment, though displacement can 25 is arranged in the deoxidation nitrogen service 16, also displacement can 25 can be arranged in the reducing gas discharge line 20.So long as the pipeline that gas flows out from jar 8, displacement can 25 can be arranged on any place so.
Above situation also is suitable in other execution mode.
(execution mode 3)
Fig. 3 is the structured flowchart of the fuel cell generation of explanation embodiments of the present invention 3.In execution mode 3, the deoxidation nitrogen service 16 between cut-off valve 17 and jars 8 has as the normal temperature jar 26 of second jar with as the cut-off valve 27 of second cut-off valve midway.Deoxidation materials 15 in jars 8 jars 8 when being set at for example fuel modifying device 2 and polymer electrolyte fuel cell 1 work can be held the position of regulation of 100 ℃ temperature, different therewith, it is the position of room temperature that normal temperature jar 26 is set at normal temperature jar 26 inside and outside temperature.
Below provide the work example.The reduction and the deoxidation treatment that are filled in the deoxidation material 15 in the jar 8 are identical with the situation of execution mode 1.In order to make deoxidation material 15 reduction, only the stipulated time in fuel modifying device 2 courses of work, open cut-off valve 18 and cut-off valve 21, close cut-off valve 14, cut-off valve 17 and cut-off valve 27.During such state, be supplied to jars 8 based on the part of the fuel gas of hydrogen.Deoxidation material 15 utilizes fuel gas to reduce, and recovers the function as deoxidation material 15.
After deoxidation material 15 reduction, close cut-off valve 18 and cut-off valve 21, open cut-off valve 14, with compressor 13 compressed air, supplying tank 8.Air supply reaches upper limit pressure, for example till 10 atmospheric pressure, compressor 13 is stopped until jar 8, closes cut-off valve 14.The air that supplies in the jar 8 utilizes deoxidation material 15 to carry out deoxidation treatment, is left to be the deoxidation nitrogen of main component and to be stored within the jar 8 with the nitrogen as inactive gas.
Carried out fully opening cut-off valve 27 after the deoxidation treatment, made the pressure of jar 8 and normal temperature jar 26 even, deoxidation nitrogen has been assigned in two jars.Then, close cut-off valve 27 again, open cut-off valve 14, with compressor 13 compressed air, supplying tank 8.Air supply is till jar 8 reaches upper limit pressure, compressor 13 is stopped, closing cut-off valve 14, open cut-off valve 27 after the deoxidation treatment, make the work of the pressure equalization of jar 8 and normal temperature jar 26 repeatedly, can ensconce in jar 8 and the normal temperature jar 26 near the deoxidation nitrogen storage of upper limit pressure.
Under same storage pressure, the gas temperature that is stored in the jar 8 is high more, and the reserves of the deoxidation nitrogen of the per unit volume of jar are more little.In the present embodiment, jar 8 the temperature of using in deoxygenation is than under the high situation of room temperature, can make as jars 8 and the deoxidation nitrogen amount that can store of the per unit tankage size of the aggregate capacity of normal temperature jar 26 more.In addition, the volume ratio of 26 pairs of jars 8 of normal temperature jar is big more, and its effect is good more.
Replenishing of vacuum suction that deoxidation nitrogen that can will make like this and be in store is used for the displacement of inactive gas of fuel cell generation and system when stopping.
Owing to have normal temperature jar 26, thus in jar 8 deoxidation material 15 reducing or jars 8 in deoxygenation situation about can not carry out fully under, also can use deoxidation nitrogen, have the high effect of the utilization degree of freedom of fuel cell generation.
In addition, after the reduction of above-mentioned deoxidation material 15, the imflammable gas composition remains in the jar 8.Here, in oxygen-containing gas supplying tank 8 before, open cut-off valve 27 and cut-off valve 21, the deoxidation nitrogen that are stored in the normal temperature jar 26 are flow in jars 8, can prevent that imflammable gas and oxygen-containing gas from mixing, and can realize safer work.
Claims (12)
1. a fuel cell generation has: the fuel cell that uses hydrogen to generate electricity; Hydrogen is supplied with the hydrogen feed unit of this fuel cell; Deoxidation material is equipped with in inside, and stored gas and meanwhile with the oxygen in the gas remove the jar; Oxygen-containing gas is boosted and supply with above-mentioned jar boosting unit; The inactive gas pipeline that above-mentioned fuel cell or above-mentioned hydrogen feed unit at least one and the above-mentioned jar among both coupled together; And be arranged on this inactive gas pipeline cut-off valve midway.
2. fuel cell generation according to claim 1, it is characterized in that: above-mentioned hydrogen feed unit is the fuel modifying device that will be behind the fuel modifying generates hydrogen, above-mentioned inactive gas pipeline with above-mentioned jar with above-mentioned fuel cell or above-mentioned fuel modifying device at least one couple together.
3. according to claim 1 or the described fuel cell generation of claim 2, it is characterized in that: have the hydrogeneous gas that to produce in the fuel cell generation and be directed to reducing gas pipeline in above-mentioned jar.
4. according to claim 1 or the described fuel cell generation of claim 2, it is characterized in that: utilize the heat that takes place in the fuel cell generation, make above-mentioned jar reach the temperature conditions of regulation.
5. according to claim 1 or the described fuel cell generation of claim 2, it is characterized in that having: the piezometry unit of measuring the gas pressure in above-mentioned jar; And, judge the computing circuit of the replacing necessity of above-mentioned deoxidation material according to the pressure decrease speed of measuring by this piezometry unit.
6. according to claim 1 or the described fuel cell generation of claim 2, it is characterized in that: have and be connected gas from above-mentioned jar of pipeline that flows out, accumulate the displacement can of condensed water.
7. according to claim 1 or the described fuel cell generation of claim 2, it is characterized in that having: the reducing gas that will be used for removing the oxygen that is included in above-mentioned deoxidation material is directed to the reducing gas pipeline in above-mentioned jar; And for above-mentioned reducing gas is imported off and on above-mentioned jar in, and be arranged on the ducted reducing gas cut-off valve of above-mentioned reducing gas.
8. according to claim 1 or the described fuel cell generation of claim 2, it is characterized in that: have and be arranged on than being arranged on second jar of the more close above-mentioned jar side of above-mentioned inactive gas pipeline above-mentioned cut-off valve midway and being arranged on second cut-off valve between above-mentioned second jar and above-mentioned jar; Make above-mentioned second jar temperature lower, open above-mentioned second cut-off valve, will in above-mentioned jar, carry out the gas of deoxidation treatment and distribute to above-mentioned second jar than above-mentioned jar.
9. fuel cell generation according to claim 8 is characterized in that: after removing the above-mentioned deoxidation material of oxygen in above-mentioned jar, with the above-mentioned jar of interior gas of gas displacement in above-mentioned second jar.
10. according to claim 1 or the described fuel cell generation of claim 2, it is characterized in that: supply with at least a portion of above-mentioned jar gas after above-mentioned boosting unit is boosted, become its oxygen concentration gas lower that in fuel cell generation, produces than oxygen concentration of air.
11. a fuel cell generation has: the interior deoxidation material that is created on the inactive gas that uses in the fuel cell generation of having adorned, in inventory of gas, remove the jar of oxygen in the gas; And oxygen-containing gas is boosted, supply with above-mentioned jar boosting unit.
12. fuel cell generation according to claim 11 is characterized in that: have the reducing gas that is contained in the oxygen that above-mentioned deoxidation material comprised in above-mentioned jar in being used to remove is supplied with above-mentioned jar reducing gas pipeline.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005114758A JP2006294466A (en) | 2005-04-12 | 2005-04-12 | Fuel cell power generation system |
| JP2005114758 | 2005-04-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1848499A CN1848499A (en) | 2006-10-18 |
| CN100409476C true CN100409476C (en) | 2008-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510109934XA Expired - Fee Related CN100409476C (en) | 2005-04-12 | 2005-09-20 | Fuel cell power generating system |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20060228611A1 (en) |
| JP (1) | JP2006294466A (en) |
| CN (1) | CN100409476C (en) |
| DE (1) | DE102005052535B4 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4616878B2 (en) * | 2007-12-14 | 2011-01-19 | 三菱重工業株式会社 | Gas engine system control method and system |
| DE102014202574A1 (en) * | 2014-02-12 | 2015-08-13 | Bayerische Motoren Werke Aktiengesellschaft | The fuel cell system |
| CN110382103B (en) * | 2017-05-11 | 2022-07-22 | 株式会社堀场Stec | Liquid material vaporization supply apparatus and computer-readable storage medium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0244654A (en) * | 1988-08-04 | 1990-02-14 | Fuji Electric Co Ltd | Gas replacement method for fuel cell |
| JP2002034102A (en) * | 2000-07-14 | 2002-01-31 | Fuji Electric Co Ltd | Fuel cell vehicle and method of stopping reformer therefor |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0410360A (en) * | 1990-04-25 | 1992-01-14 | Fuji Electric Co Ltd | Fuel cell power generating device |
| JPH06203864A (en) * | 1993-01-06 | 1994-07-22 | Sanyo Electric Co Ltd | Fuel cell system |
| JPH06203865A (en) * | 1993-01-06 | 1994-07-22 | Sanyo Electric Co Ltd | Fuel cell system |
| JPH0729589A (en) * | 1993-07-09 | 1995-01-31 | Ishikawajima Harima Heavy Ind Co Ltd | Differential pressure control method of plate type reformer in fuel cell power generating system |
| JPH07169493A (en) * | 1993-12-17 | 1995-07-04 | Toshiba Corp | Combustible gas purge device for fuel cell power plant |
| JPH07320767A (en) * | 1994-05-27 | 1995-12-08 | Toshiba Corp | Fuel cell power plant |
| JPH11191426A (en) * | 1997-12-26 | 1999-07-13 | Sanyo Electric Co Ltd | Fuel cell power generating system |
| JP2000277137A (en) * | 1999-03-24 | 2000-10-06 | Matsushita Electric Works Ltd | Method for purging residual gas from fuel cell power generating system |
| JP2002050372A (en) * | 2000-08-04 | 2002-02-15 | Honda Motor Co Ltd | Fuel cell purge device |
| JP2002110207A (en) * | 2000-10-03 | 2002-04-12 | Nippon Mitsubishi Oil Corp | Fuel cell system and operation method therefor |
| JP2002280038A (en) * | 2001-03-21 | 2002-09-27 | Matsushita Electric Ind Co Ltd | Fuel cell electric power generating system |
| JP2003089505A (en) * | 2001-09-11 | 2003-03-28 | Aisin Seiki Co Ltd | Reforming apparatus and fuel cell system |
| DE10164755B4 (en) * | 2001-10-25 | 2005-03-17 | Daimlerchrysler Ag | Gas generation system |
| CN100336259C (en) * | 2002-05-02 | 2007-09-05 | 三菱重工业株式会社 | Fuel cell power generation system and method for operating the same |
| JP2003327408A (en) * | 2002-05-10 | 2003-11-19 | Mitsubishi Electric Corp | Fuel treatment apparatus and operation method thereof |
-
2005
- 2005-04-12 JP JP2005114758A patent/JP2006294466A/en active Pending
- 2005-09-20 CN CNB200510109934XA patent/CN100409476C/en not_active Expired - Fee Related
- 2005-11-03 DE DE102005052535A patent/DE102005052535B4/en not_active Expired - Fee Related
- 2005-11-30 US US11/289,566 patent/US20060228611A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0244654A (en) * | 1988-08-04 | 1990-02-14 | Fuji Electric Co Ltd | Gas replacement method for fuel cell |
| JP2002034102A (en) * | 2000-07-14 | 2002-01-31 | Fuji Electric Co Ltd | Fuel cell vehicle and method of stopping reformer therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102005052535A1 (en) | 2006-10-19 |
| JP2006294466A (en) | 2006-10-26 |
| CN1848499A (en) | 2006-10-18 |
| US20060228611A1 (en) | 2006-10-12 |
| DE102005052535B4 (en) | 2011-04-21 |
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